Bis (p-aminophenyl) butadiene and derivatives



, specifically, it relates to 1,4-bis(para-arninophenyl)- United States Patent ice 2,852,556

Patented Sept. 16, 1958 expectation that the dyes derived from diphenylbutadiene 2,852,556 would be much more unstable. This however is not observed. Increase in conjugation normally has the elfect i F i% g AND of shifting the color of compounds into the visible. Many 5 stilbene brighteners are already pale yellow and it was Leon Katz, Westfield, Delton W. Hein and John E. Pretka, expected that the 1,4-diphenylbutadiene compounds would Sunnia Rhhelt Lollg, Bound Brook, N= -9 have a pronounced color in the visible. We were thereassighors to Amefieah cyahamid New Ymk? fore very much surprised to find that this was not so, a corpomnon of Mame and that the 1,4-bis(para-acylaminoand alkylamino- N0 Drawing. Application September 7, 1954 10 henyDbutadienes are still relatively uncolored.

Serial No. 454,642 Substant1v1ty is believed in the art to be a function of hydrogen bonding between the dye and the fiber and is therefore a function of the relative geometry of the fiber and dye molecules. The increase in the chain length of the butadiene derivatives of our invention over the corresponding stilbene derivatives made it unpredictable that the compounds of our invention would be substantive. They are in fact, however, quite substantive.

For certain uses where water solubility is important derivatives can be prepared in which a carboxy group is 12 Claims. (Cl. 260518) This invention relates to new intermediates and to the 15 dyes, pigments and brighteners derived therefrom. More butadienes, to 1,4-bis(para-aminophenyl)butadiene-l-carboxylic acid and -1,4-dicarboxylic acid, to the corresponding acyl and alkylamino compounds, and to azo dyes and Pigments derived from the free elhlho compoundssubstituted on the butadiene chain. In other cases, where T e hutedlehe y has P F P Y been known In such solubility is not desired, as for example in pigments y chemistry y 111 eertalh 151eted cases such as and brighteners for non-cellulosic fibers, the best interthe light-Sensitive eyahihe y Whleh are used as P mediate is a 1,4-bis(para-aminophenyl)-1,3-butadiene sensitizers and desensitizers. f f carboxy groups,

We have f d th (Pe P y Uncarboxylated products are prepared by the condensat di s and their Ting suhstihlheh predhefs are 3 tion of a p-acylaminobenzaldehyde with succinic anhydride i t rm ia s the Preparatieh ef y Pigments and to give a 1,4-bis(p-acylaminophenyl) 1,3-butadiene which brighteners, and that the various coloring matters thus may be hydrolyzed to the free amino compound. Al obtained have excel e t pr p e The eeylamlho and natively, a p-nitrobenzaldehyde is condensed with sucalkylamino derlvatives of the diphenylbutadiene system i i anhydride, and the resultant l,4-bis(p-nitrophenyl) fillefesee and are e hrightehel's- The azo derivatives 1,3-butadiene on reduction yields the same compound. Obtained from 1,4-h1s(pafa-emlhophehyl)hutadlehe are If desired, this can then be acylated to give an acyl degeed y of shades Which in y Cases are unusually rivative. There are thus two alternative routes available deep and very useful. to either the acylamino or the aminophenylbutadienes and Flu r s n alone is not enough t0 make good bright the choice of the route will depend on the circumstances. eners. The compound must also be substantive to the If h l g gup i h h i 111 b ff d b th cloth, must be itself relatively uncolored, and must fiuoreaction conditions, the procedure starting with an acylresce in the visible in the blue range in order to cancel aminobenzaldehyde i th b t one t use t bt i an out the natural Yellow of the eleth- While p y 4O acyl derivative. Where the acyl group may be afiected b di i uncolored, the addition of the strongly auxoan alternative route is chosen. These reactions can be chromic amino groups would have been expected to proillustrated by the following equations:

NHr-O-OH==TH NH2CH=CH CHa-CO\ NO on=cn /H zNokQono I I Ont-00 NOOCH=CH duce color in the molecule. It is unexpected to find that Carboxylated products are made by modification of the corresponding acylamino and alkylamino derivatives the above procedures using slightly different intermedinot only are relatively uncolored but that they possess ates. A mono-carboxy derivative is prepared by the congood substantivity to the cloth, fluorescence in the blue densation of p-nitrocinnamaldehyde on p-nitrophenyl range of the visible, and have good fastness properties. acetic acid. The resultant 1,4-bis(p-nitrophenyl)-l,3- These properties would not be predicted. butadienel-carboxylic acid is readily reduced to the cor- While stilbene compounds have been used in dyes and responding amino compound. A 1,4-bis(p-aminobrighteners, there were definite reasons to expect that the phenyl)-1,3-butadiene-1,4-dicarboxylic acid is prepared diphenylbutadiene structure would be unusable. The by the condensation of glyoxal with a p-nitrophenyl acetic high reactivity of the butadiene system leads one to an acid followed by reduction to the free amine. These various amino compounds are acylated to give the corresponding acylamino compounds. These reactions may be represented as follows:

COOH

moGom +030 coon c011 and halogen derivatives thereof, 2-4-dinitrocinnamaldehyde, 2-carboxy-4-nitrocinnamaldehyde and similar compounds and para-nitrophenyl-acetic acid, 2-chlor-4-nitrophenylacetic acid, 3-hydroxy-4-nitrophenylacetic acid and 3-methoxy-4-nitrophenylacetic acid and the like. In the case of the mono carboxy derivatives unsymmetrical derivatives can be prepared by the proper choice of the nitro cinnamaldehyde and nitro phenyl acetic acidto be used.

The acylamino derivatives of 1,4-bis(p-aminophenyl)- butadiene fluoresce and are readily usable as brighteners.

.As: acyl, groups onecan use-the benzoyl group; alkylbenzoyl groups, such as o-toluyl, p-toluyl; alkoxybenzoyl groups, such as p-anisoyl, o-ethoxybenzoyl, 2,4-dimethoxybenzoyl, 2,5-diethoxybenzoyl and the like; amino derivatives suchas p-aminobenzoyl; halogen derivatives such as 'p-chlorobenzoyl', 2,4-dichlorobenzoyl, and the like; or aliphatic acyl derivatives such as formyl, acetyl, propionyl, butyryl' and. the like. These acyl derivatives may be prepared either from the 1,4-diphenyl butadiene from the corresponding diphenyl butadiene carboxylic acids or from nuclear substitution products of any ofthese.

Alkyl derivatives of these amino compounds also fluoresce. Those without carboxy groups are especially good brighteners for non-cellulosic fibers. They are either prepared: by the alkylation of 1,4-bis(p-aminophenyl)-l,3-butadiene or by synthesis starting with dialkylaminobenzaldehyde in the place of the acylaminobenzaldehyde. Alkylation of the aminophenylbutadiene can be carried outeither by the use of alkyl sulfates: or alkyl halides. Lower alkyl derivatives are best prepared by the use. of the dialkyl sulfates while the alkyl; halides are more available in the case of. the higher alkyl groups. When mono-alkyl derivatives are desired, they are-.prepared bysynthesis starting with an a means to obtain very greenish blue shades whic acylated monoalkyl amino benzaldehyde which is condensed with succinic anhydride followed by deacylati'om We have further found that azo dyes and pigments of interesting properties are preparable by the tetrazotization of the bis(aminophenyDbutadienes followed by coupling to the usual coupling components. The bis(amino-' phenyDbutadienes are especially good as- Fast Baseswhen coupled into naphthols such as the arylides of beta-oxyw naphthoic acid. One can also couple-to sulfonatedcom pounds such as naphthol sulfonic. acids or amino naphtho sulfonic acids to produce. direct dyes. Among these-cou-f pling components are 1,-naphthol-2-sulfonic acid, l-i naphthol-2,7-disulfonic acid, 2-naphthol-4-sulfonic acid, 2-naphthol-3,6-disulfonic, acid, 2 -naphthol-3',6,8'-trisulfonic acid, S-amino-1'-naphthol-5',7 disulfonic acid, 8- amino-1-naphthol-3,6-disulfonic acid, and, the like. The preparation of direct dyes is not limited to naphthols since, any other sulfon'ated coupling component can equally be. used. With relation, to the; direct dyes-, was obviously not; predictable whether increase in, th length of the molecule would have a harmful died. on; the substantivity of the dyes for cellulosic materials. We have found in fact that the substantivity is; notimpaired.

We have. also found that the butadiene structure ha. a. bathochromic effect on the shade when compared-(with dyes from the corresponding stilbenes orbenzidines This is a. veryimportant observation since. itprovide cannot normally be obtained. with, simple azo dyes. This is particularly true of dyes derived from, l,4-bis.(3, methoXy-4-aminophenyl)butadiene and related com. pounds. These dyes are of particular interestHbecaus the. methoxy. groups permit metallization; when the'cou'r pling component hasv metallizable groups, such as; by, droxyl or amno ortho to the azo group,, .-nd; metallization generally leads to, improved fastness' tQJight. Dyg ofi this typemay be represented. as follows;

where R is the residue of coupling component. amples of coupling components which may be used: are beta naphthol, 3-hydroxy-2-naphthoic arylides, 2+naphthol-6-sulfonic acid, 2-naphthol-3,6-disulfonic. acid,.-2: naphthol-6,8-sulfonic acid, 7-amino-1-naphthol-3-sulfonicacid; and the like.

Our invention can be illustrated by the following ex? amples in which parts are by Weight unless otherwise specified.

Example 1 0 o ll om-o-rmQomorromen-@rm-ii-om A mixture of 89.5 parts of p-acetaminobenzaldehyde,, 27.5 parts of succinic anhydride, 57.5 parts of litharge, and 75 parts of acetic anhydride is stirred at the boil until the condensation is complete. It is then cooled and diluted with. 75parts of acetic acid followed by parts of methanol. The precipitated product is then isolated by filtration and reslurried in 250 parts of methanol. This slurry is boiled, cooled, and filtered. The product ob- I tained is 1,4-bis(p-acetaminophenyl)butadiene. It can be recrystallized from nitrobenzene and other solvents to give asample of good analysis for this compound.

By starting with p-benzamide benzaldehyde, p-(2-meth oxy-4-methylbenzoylamino)benzaldehyde, or p-(2,5-diethoxybenzoylamino)"benzaldehyde, the corresponding 1...,- 4-bis(p-acylaminophenyl)butadienes are formed. f

By starting with 4-acetamido-2-chlorobenzaldehyde, 4 V acetamido-2,6-dichlorobenzaldehyde, 4-acetamidor2 nitroe benzaldehyde, 4-acetamido-3-methylbenzaldehyde or [4 1 acetamido-3-rnethoxybenzaldehyde, the corresponding 1,4'

,reaction ,is -:substa ntial'ly complete.

bis(acetamidophenyl)butadienes, further substituted in the aromatic rings are formed.

Example 2 'istransformed to the free base by dissolving in hot water,

alkalizing, and isolating in the usual Way. The solid, identical to the product produced by the procedure of tallizati on ii-om toluene giving brownish-yellow granules.

Example 3 COOH 4.53 parts of'p-nitrophenyl lacetic1acid' andl2.75 parts of litharge are thoroughly-mixed. The mixture is then slurriedin 20 parts ofacetic'anhydride and the slurry is heated toboiling. 4.43 parts ofgp-riitro-cinnamaldehyde is added: andthelmixture is heated at theboil until separates, is isolated by filtration and washing.

6 purified by reprecipitation from sodium carbonate solution with acid.

Example 5 COOH 00011 5.6 parts or" sodium hydroxide is dissolved in 100 parts of water. 7.24 parts of p-nitrophenyl acetic acid is added and the solution is cooled. 3.86 parts of 30% aqueous glyoxal is then added and the mixture is stirred at 0 C. for a short time followed by stirring at room temperature until the reaction is substantially complete. The product is isolated by filtration and dissolved in boiling Water. The solution is salted with saturated brine and cooled to room temperature. The light yellow orange solid, which It is the disodium salt of 1,4-bis(p-nitrophenyl)-l,4-bis(carboxy)- 1,3-butadiene.

Substituted 1,4-bis (p-nitrophenyl) -1,4-bis(c;arboxy) 1,3- butadienes in which the aromatic ring are correspondingly substituted, are obtained when there is substituted for the p-nitrophenyl acetic acid equivalent amounts of 2-chloro- 4-r1itro-phenylacetic acid, and 3-methoxy-4-nitrophenyl acetic acid.

Example 6 The procedure of Example 4 is followed, using 1.16 parts of the product of Example 5 instead of 1.0 part of the product of- Example 3. The product is 1,4-bis- (p-aminophenyl) -1,4-bis (carboxy) 1,3-butadiene.

Example 7 The precipitated product is filtered hot and-washed with water. The rude product may be purified by reprecipitation from sodium carbonate solution with acid and can also be recrystallized from, acetic acid. It is 1,4-bis(p-nitrophenyl)-1-carboxy- 1,3-butadiene.

When an equivalent quantity of 2,4-dinitrophenylacetic acid is used, one. obtains,1-(2,4dinitrophenyl)-4- t (4-nitrophenyl) -lecarboxyelfi-butadiene.

Example 4 OOH Example 8 One part of the product, of Example .3 isslurried in 25 parts of concentratedammonia and-thernixture is heated ,to the boil. Five parts of ferrous-sulfate are added graduallyandthereaction mixture is boiled until the reduction is substantially complete. The mixture is v clarified by. filtratiomand-the filtrateislcarefully neutralized with dilute hydrochloric acid. The precipitated product is isolated by filtration and washing. It may be The procedure of Example 7 is followed using 28 parts of the product of Example 3 to give 1,4-bis(p-benzoyl- Example 9 i OOH COOH The procedure of Example 7 is followed using 32.4

parts of the product of Example to give 1,4-bis-(benzarn-idophenyl)-l,4dicarboxy butadiene.

Similarly, equivalent amounts of other acid chlorides such as anisoyl chloride, o-ethoxybenzoyl chloride and 2,4-dimethoxybenzoyl chloride may be substituted for the vbenzoyl chloride to give the corresponding alkoxy- 5 benzamido butadiene dicarboxylic acid.

A mixture of 23.6 parts of the product of Example 6 with 250 parts of water and parts of sodium carbonate is alkylated with excess dimethyl sulfate, sodium hy- HzN OH Example 11 The procedure of Example 1 is followed, substituting 83 .parts of p-nitrobenzaldehyde for the acetylaminobenzaldehyde.

The resultant 1,4-bis(p-nitrophenyl)-butadiene can be reduced by the procedure of Example 4 to give a product identical with that of Example 2.

Example 12 I The, procedure of Example 1 is followed, using 228 parts of p-octadecylacetaminobenzaldehyde (prepared by treating p-arninobenzaldehyde with octadecyl bromide,

followed by acetylation) in place .of acetaminobenzal'dehyde. The resulting 1,4-bis(p-octadecylacetaminophenyl)butadiene is hydrolyzed by the procedure of Example 2 to give 1,4-bis(p-octadecylaminophenyl)butadiene.

By using the similarly prepared p-butylacetaminobenzaldehyde in place of the octadecyl compound, 1,4-bis(pbutylaminophenyl)butadiene is prepare Example 13 The product of Example 2 is, tetrazotized in the usual manner. Cotton cloths previously printed with pastes of 7. 1,4-bis-acetamidophenylbutadienes, in which the sail .least one of the terminal carbon atoms is substituted by 8 naphthols prepared in the usual manner are dyedwiiis" the tetrazo solution. The following colors are obtained 3-hydroxy-2-naphth0ic anilld enlui reddish-blue 2-methy1-3-hydroxy-2-naphthoic anilide Do. 4,4-bis(acetoacetamido)3,3-dimethy1 biphenyL. yellow-cram 2 ,5 -dimeth0xy-3-hydroxy-Z-naphtholc anilide maroon.

3-nitro-3-hydroxy-2-naphthoic anilide reddish-blue. 2-ethoxy-3-hydroxy-2-naphth0lc anilide blue. 2-methyl-4-methoxy-2-hydroxy-1l-benzo(a)carbazole-3- yellow-gray. earboxanilide. I j. z-acetoacetamido-fiethoxy benzothlazole reddlsh tan.

7 Example 14 A'suspension of 1.08 parts of 1,4-bis(p-aminophenyl 1,3-butadiene in 25 parts of water strongly acidifiedwifls hydrochloric acid was tetrazotized in the usual fashi i at 10 C. The tetrazosolution was clarified and add portionwise to a solution of 2.86 parts of 2-naphthol-3,6- disulfonic acid disodium salt in 50 parts of water contain ing 0.4 part caustic. The mixture was stirred until cou; pling was essentially complete, with additions of sod;. ash when necessaryto maintain a positive test on Brih liant Yellow paper. The coupling product was isolated and purified further by reprecipitating it from a' solution in dilute caustic by addition of sodium acetatecrystaln,

The dye exhausted rapidly onto. cotton. givinga .b l' shade, appreciable greener in hue than the correspon dyes from 4,4'-diaminostilbene and benzidine.

Example 15 0H NH] The procedure (if-Example 14 is followed substituting an equivalent amount of Chicago acid (l-amino-S-naphthol-2,4-disulfonic acid) for R-salt (2-naphthol-3,6-disul fonic acid). The product dyes cotton and rayon at attractive greenish-blue shade, greener than that. from the dye of Example 14. Y

We claim:

1. 1,4-bis(p-aminophenyl)butadienes in which the said butadiene chain is otherwise unsubstituted except when at a carboxyl group. 2. 1,4-bis(p-aminophenyl)butadiene. 3. 1,4-bis(p-aminophenyl)butadienes, in which the butadiene chain hasa carboxyl group attached to at lead one of the terminal carbons, the said butadiene chain being otherwise unsubstituted. p 4. 1,4-bis (p-aminophenyl)butadiene-l-carboxylic acid. 5. 1,4-bis(p-aminophenyDbutadiene 1,4 dicarboxylic acid. 6. 1,4-bis-acylaminophenylbutadienes in which thesaill butadiene chain is' otherwise unsubstituted except wh'cn at least one of the terminal carbon atoms is substituted by a carboxyl group, and in which the said acyl group is chosen from the group consisting of benzoyl, lower alkylbenzoyl, lower-alkoxybenzoyl, aminobenzoyl, chloe robenzoyl, and lower alkanoyl.

butadiene chain is otherwise unsubstituted except when at least one of the terminal carbon atoms is substituted by a carboxyl group.

11. The compound of the formula GOOH OOH C CH CH;

8. 1,4-bis-monoalkylaminophenylbutadienes, in which 1 and its soluble salts.

12. 1,4-bis(p-substituted phenyl)butadienes in which said para substituent is selected from the group consisting of amino, benzoylamino, lower-alkylbenzoylamino, lower alkoxybenzoylamino, aminobenzoylamino, chlorobenzoylamino and lower-alkanoylamino, and alkylamino,

the said butadiene chain being otherwise unsubstituted except when at least one of the terminal carbon atoms is substituted by a carboxyl group.

onto CO-NH-?=GHCH=CH -NH--CO 0GH| COOH CH5 CH5 and its soluble salts.

References Cited in the file of this patent -,UNITED STATES PATENTS 2,098,782 Hopfii et a1. Nov. 9, 1937 2,537,950 Allen Jan. 16, 1951 2,624,757 Bersworth Jan. 6, 1953 2,660,606 Newby Nov. 24, 1953 2,665,309 Bruce Jan. 5, 1954 

1. 1,4-BIS(P-AMINOPHENYL)BUTADIENES IN WHICH THE SAID BUTADIENE CHAIN IS OTHERWISE UNSUBSTITUTED IN WHICH THE SAID LEAST ONE OF THE TERMINAL CARBON ATOMS IS SUBSTITUTED BY A CARBOXYL GROUP. 